Microcapsule having a microcapsule shell material that is rupturable via a retro-dimerization reaction

ABSTRACT

A microcapsule encapsulates a payload agent, the microcapsule having a microcapsule shell material that is rupturable (e.g., to release the encapsulated payload agent) via a retro-dimerization reaction.

BACKGROUND

Microcapsules may be used as release systems for various types ofmaterials (also referred to as “payloads”). Examples of payloads includeperfume oils, repellants, self-healing agents, or disinfectants, amongother alternatives. Rupturing the microcapsule, and release of thepayload, may depend on mechanically breaking a polymer shell of themicrocapsule. For example, the polymer shell may be broken byscratching, puncturing, or other mechanical means directly applied to apolymeric surface of the microcapsule.

SUMMARY

According to an embodiment, a process includes functionalizing adimerizable molecule to form a functionalized material. The process alsoincludes dimerizing the functionalized material to form a dimerizedmaterial with orthogonal functionality. The process further includesutilizing the dimerized material with orthogonal functionality duringformation of a microcapsule that encapsulates a payload agent.

According to another embodiment, a process is disclosed that includesrupturing a microcapsule shell material of a microcapsule to release anencapsulated payload agent via a retro-dimerization reaction.

According to another embodiment, a microcapsule that encapsulates apayload agent is disclosed. The microcapsule has a microcapsule shellmaterial that is rupturable via a retro-dimerization reaction.

The foregoing and other objects, features and advantages of theinvention will be apparent from the following more particulardescriptions of exemplary embodiments of the invention as illustrated inthe accompanying drawings wherein like reference numbers generallyrepresent like parts of exemplary embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram depicting a process of preparing a microcapsule(having an encapsulated payload) containing an orthogonal functionality,according to one embodiment.

FIG. 2 is a chemical reaction diagram illustrating a process of forminga dimerized material with orthogonal functionality for use duringformation of the microcapsule depicted in the example of FIG. 1,according to one embodiment.

FIG. 3 is a chemical reaction diagram illustrating a process ofretro-dimerization that results in rupture of the microcapsule shellmaterial and associated release of the encapsulated payload agent(s),according to one embodiment.

FIG. 4 is a flow diagram showing a particular embodiment of a process offorming a polymeric material that includes microcapsules withencapsulated payload agent(s) that may be released via aretro-dimerization reaction.

DETAILED DESCRIPTION

The present disclosure describes processes to generate anano/microcapsule system that releases the payload content based onretro-dimerization. Additionally, the capsules can be subjected tomechanical breaking using substantially greater mechanical force due tothe microcapsule shell material disclosed herein. Further, the presentdisclosure describes the incorporation of orthogonal functionalitiesthat can covalently bind into a polymer matrix, thus allowing for moresensitive detection of cracks in the polymer matrix. Thesenano/microcapsules can be generated with homogeneous size distributionsto prevent leach out of the encapsulated payload, bind directly into apolymer matrix, and can be utilized as a functional filler to strengthena composite material. Such microcapsules may be utilized in multipleapplications.

As used herein, the term “microcapsule” is used to refer to capsulesthat are in a range of about 10 microns to 1000 microns in diameter.However, it will be appreciated that the following disclosure may beapplied to capsules having a smaller size (also referred to as“nanocapsules”). In the present disclosure, a payload (or multiplepayloads) may be incorporated into a polymeric microcapsule that isgenerated containing dimer blocks. Further, the dimer-containing blockscan have orthogonal functionality, affording the ability to covalentlybind to a polymeric matrix. After incorporation of these microcapsulesinto the polymer matrix, the capsules may be ruptured viaretro-dimerization. In some cases, the microcapsules may be ruptured viamechanical means to release the encapsulated payload, and themicrocapsule shell material may degrade via retro-dimerization (e.g.,via exposure to sunlight).

Several advantages are associated with the subject matter of the presentdisclosure. For example, the microcapsules of the present disclosureallow for a homogeneous distribution of payload agent(s), theincorporation of microcapsules at various volumes depending on theamount of payload agent(s) that are desired, and the ability for themicrocapsules to covalently bind directly into a polymeric resin. Asanother example, the microcapsules of the present disclosure may be usedas a flow controller and assist and/or eliminate nano-silica. Themicrocapsules may be generated in a homogeneous size, thus allowing fora controlled release of payload agent(s) per unit area. Further, themicrocapsules may be considered environmentally friendly due to theprotective packaging of the microcapsule in order to prevent leach outof the payload agent(s). As a further example, the microcapsules of thepresent disclosure represent functional fillers that increase mechanicalproperties. It will be appreciated that the advantages described aboveare for illustrative purposes only and other advantages may beassociated with the utilization of the microcapsules of the presentdisclosure in various contexts.

In the present disclosure, payload-containing microcapsules containingan orthogonal functionality may be manufactured using an oil-in-wateremulsion technique to create a protective polymeric shell around apayload agent core. In a particular embodiment, (orthogonal functional)resveratrol that is dimerizable replaces standard resorcinol in themicrocapsule synthesis process.

To illustrate, in a process of preparing the microcapsules of thepresent disclosure, a dimerizable molecule undergoes bonding to generatea resorcinol-like monomer. An illustrative, non-limiting example of adimerizable molecule includes resveratrol. One advantage associated withthe use of resveratrol is that resveratrol is a naturally occurringbio-based material, thus increasing the renewable bio-based content ofthe associated microcapsules. Other dimerizable molecules may beselected by one of ordinary skill in the art.

A payload agent acts as the oil phase that is dispersed into an aqueouscontinuous phase and stirred, thus beginning the emulsion process. Oneexample of a payload agent that could be used is a latent curing agentsuch as n-ethylpiperazine. Other payload agent(s) may be selected by oneof ordinary skill in the art. One area of possible payloads could bepolymerizable molecules such as cyclic olefins, norbornene, substitutednorbornene, cyclooctadiene, substituted cyclooctadiene, lactones,acrylates, acrylic acids, styrenes, isoprene, butadiene, isocyanatefunctional groups with hydroxyl functional groups, and epoxies. Suchagents typically require an activator such as a catalyst and/or aninitiator, which can be selected by one of ordinary skill in the art.Additionally, solvents could be incorporated into the microcapsules,including aprotic solvents, protic solvents, or combinations thereof.

A cross-linking agent is then used to react with a polymeric emulsifyingagent to generate the capsule wall around the payload agent(s). Particlesize may be controlled by adjusting a stir speed of the reaction (e.g.,the higher the stir speed, the finer the particles). Finally, a curingstep is used to complete the reaction between the cross-linking agentand the polymeric emulsifying agent to form the microcapsule. Theresulting microcapsules may then be incorporated into a polymer matrix,with the microcapsules covalently binding to the polymer matrix. Theamount of microcapsules to be utilized may be empirically determinedbased on the rheology of the polymeric resins, the microcapsule particlesize, and the amount that is sufficient to reach the desired payloadcontent for release.

FIG. 1 is a diagram 100 depicting an example of the preparation of amicrocapsule (having an encapsulated payload) containing an orthogonalfunctionality. FIG. 2 depicts an example of the preparation of aresveratrol dimer with an orthogonal functionality for use in theformation of the microcapsule depicted in FIG. 1. In FIG. 1, the payloadfilled microcapsules containing the orthogonal functionality are formedusing an oil-in-water emulsion technique to create a protectivepolymeric shell around a payload core. As illustrated and furtherdescribed herein with respect to FIG. 3, after incorporation of themicrocapsules into a polymer matrix, the microcapsules may be rupturedto release the payload via retro-dimerization of theresveratrol-containing groups.

In the example of FIG. 1, a payload represents an oil phase that isdispersed into an aqueous continuous phase and stirred to begin anemulsion process. As illustrative, non-limiting examples, the payload(or multiple payloads) may include a perfume oil, a self-healing agent,a disinfectant, a repellant, or a combination thereof. It will beappreciated that various payload(s) may be selected to provide variousfunctionalities for various applications. In FIG. 1, a cross-linkingagent is reacted with a polymeric emulsifying agent to generate acapsule wall around the payload. Particle size may be controlled byadjusting the stir speed during the reaction. For example, a faster stirspeed may result in formation (on average) of smaller (“finer”)particles than a slower stir speed. FIG. 1 further illustrates that acuring stage may be used to complete the reaction between thecross-linking agent and the polymeric emulsifying agent to form themicrocapsules (or nanocapsules, depending on the stir speed).

In a prophetic example, the microcapsules containing an orthogonalfunctionality that are depicted in FIG. 1 may be prepared according tothe following process. To a stirring aqueous solution containing anethylene maleic anhydride (EMA) copolymer surfactant, urea, and NH₄Cl,the resveratrol dimerized reactant with an orthogonal functionality(depicted in FIG. 2) may be added. The pH may be adjusted to about 3.5by adding NaOH and HCl (or other acids/bases), followed by the additionof an emulsifying agent. The payload may be added with otheringredients, such as monomers and/or pre-polymers, stabilizers,solvents, viscosity modifiers, odorants, colorant/dyes, blowing agents,antioxidants, or co-catalysts, or a combination thereof. Formaldehydemay be added, which acts as a curing agent to complete the shellformation. The resulting microcapsules may be subsequently washed andsieved to remove unreacted material.

Thus, FIG. 1 illustrates an example of a process of forming amicrocapsule (having an encapsulated payload) containing an orthogonalfunctionality. As illustrated and further described herein with respectto FIG. 2, a resveratrol dimer with an orthogonal functionality may beutilized in the formation of the microcapsule depicted in FIG. 1.Additionally, as illustrated and described further herein with respectto FIG. 3, retro-dimerization of the resveratrol-containing groups(utilizing UV light) may result in rupture of the microcapsules and theassociated release of the encapsulated payload agent(s). Further, insome cases, the microcapsules may be ruptured via mechanical means torelease the encapsulated payload, and the microcapsule shell materialmay degrade via retro-dimerization (e.g., via exposure to sunlight).

Referring to FIG. 2, a chemical reaction diagram 200 depicts an exampleof a process of preparing a resveratrol dimer with orthogonalfunctionality, according to one embodiment. In the particular embodimentdepicted in FIG. 2, an allyl-functionalized resveratrol is illustrated.It will be appreciated that the allyl-functionalized resveratroldepicted in FIG. 2 represents a non-limiting, illustrative example of amaterial with an orthogonal functionality for incorporation into themicrocapsule depicted in FIG. 1. Other examples may includevinyl-functionalized resveratrol (via vinyl chloride),(meth)acrylate-functionalized resveratrol (via (meth) acryloylchloride), and epoxy-functionalized resveratrol (via epichlorohydrin)which can be used to react with the appropriate moiety in the polymericresin.

In the first chemical reaction depicted at the top of FIG. 2,resveratrol is chemically reacted with an allyl material to form anallyl-functionalized resveratrol. As a prophetic example, the firstchemical reaction may be performed in the presence of triethylamine andtetrahydrofuran (THF) at a reaction temperature of about 0° C.

The second chemical reaction depicted at the bottom of FIG. 2illustrates the dimerization of the allyl-functionalized resveratrolformed in the first chemical reaction using ultraviolet light (e.g., ata wavelength of at least 300 nm), resulting in a resveratrol dimer withan orthogonal functionality. The butene ring formation in the exampledepicted in FIG. 2 may generate a rigid molecule that may improve thestrength of a standard resorcinol-containing shell.

Thus, FIG. 2 illustrates a particular embodiment of a process ofproducing a dimerized material with an orthogonal functionality. Asfurther described herein, the dimerized material depicted in FIG. 2 maybe utilized during the formation of the microcapsule (having anencapsulated payload), as illustrated in FIG. 1.

Referring to FIG. 3, a chemical reaction diagram 300 depicts an exampleof a process of retro-dimerization that results in rupture of themicrocapsule shell material and associated release of the encapsulatedpayload agent(s). Alternatively, the microcapsules may be ruptured viamechanical means to release the encapsulated payload, and themicrocapsule shell material may degrade via retro-dimerization (e.g.,via exposure to sunlight).

The left side of the chemical reaction diagram depicted in FIG. 3illustrates that incorporation of the microcapsule with the orthogonalfunctionality depicted in FIG. 1 into a polymeric matrix material, afirst portion of the orthogonal groups are bound within the microcapsuleshell and a second portion of the orthogonal groups are bound to thepolymeric matrix material.

The right side of the chemical reaction diagram depicted in FIG. 3illustrates that UV light (e.g., at a wavelength that is less than 240nm) results in a retro-dimerization reaction. The retro-dimerization ofthe resveratrol-containing groups may result in rupture of themicrocapsules and the associated release of the encapsulated payloadagent(s). In other cases, the microcapsules may be ruptured viamechanical means to release the encapsulated payload, and themicrocapsule shell material may degrade via retro-dimerization (e.g.,via exposure to sunlight).

Thus, FIG. 3 illustrates an example of a retro-dimerization reactionthat is initiated via UV light that may result in the rupture of themicrocapsules and the associated release of the encapsulated payloadagent(s). Alternatively, as described herein, in some cases, themicrocapsules may be ruptured via mechanical means to deliver theencapsulated payload, and the retro-dimerization reaction may degradethe microcapsule shell material. In some cases, the UV light may be froma natural source (e.g., sunlight), while in other cases an end user mayapply UV light in order to initiate the rupture of the microcapsuleshell material.

Referring to FIG. 4, a flow diagram depicts an example of a process 400of forming a polymeric material that includes a microcapsule (having anencapsulated payload) having orthogonal functionality that is bonded tothe polymeric material. In the particular embodiment depicted in FIG. 4,the process 400 further includes rupturing the microcapsule shellmaterial via retro-dimerization to release the encapsulated payloadagent(s). FIG. 4 illustrates an example of a process of producing amicrocapsule that includes orthogonal functional groups (as shown inFIG. 1 and further described herein with respect to FIG. 2). FIG. 4further illustrates that the microcapsule having the orthogonalfunctionality may be blended with or applied to the polymeric material,and the microcapsule may be bonded to the polymeric material via achemical reaction of a portion of the orthogonal functional groups ofthe dimerized material (as illustrated and further described herein withrespect to FIG. 3). As described further herein with respect to FIG. 3,the microcapsules that are bonded to the polymeric material may beruptured via retro-dimerization when exposed to UV light.

In the particular embodiment illustrated in FIG. 4, operationsassociated with an example process of producing microcapsules containingorthogonal functionality are identified as operations 402-406, whileoperations associated with incorporating the microcapsules into apolymeric matrix material are illustrated as operation 408, andoperations associated with rupturing the microcapsules are illustratedas operation 410. It will be appreciated that the operations shown inFIG. 4 are for illustrative purposes only and that the operations may beperformed in alternative orders, at alternative times, by a singleentity or by multiple entities, or a combination thereof. As an example,one entity may produce the allyl-functionalized resveratrol depicted inFIG. 2, another entity may utilize the allyl-functionalized resveratrolto form the resveratrol dimer with the orthogonal functionality depictedin FIG. 2, while another entity may produce the microcapsule containingthe orthogonal functionality depicted in FIG. 1. Further, alternative oradditional entities may perform the operations associated with bondingthe microcapsule depicted in FIG. 1 to the polymeric matrix material.Additionally, another entity (or naturally in the environment as aresult of exposure to sunlight) may rupture the microcapsule shell torelease the encapsulated payload(s) and/or to degrade the microcapsuleshell after rupture via mechanical means.

The process 400 includes functionalizing a dimerizable molecule to forma functionalized material, at 402. For example, referring to the firstchemical reaction depicted at the top of FIG. 2, resveratrol may bechemically reacted with an allyl material to form anallyl-functionalized resveratrol. It will be appreciated thatresveratrol is one example of a dimerizable molecule that undergoesbonding to generate a resorcinol-like monomer and that other dimerizablematerials may be utilized in other embodiments. Further, theallyl-functionalized resveratrol depicted in FIG. 2 represents anon-limiting, illustrative example of a material with an orthogonalfunctionality for incorporation into the microcapsule depicted inFIG. 1. Other examples may include vinyl-functionalized resveratrol (viavinyl chloride), (meth)acrylate-functionalized resveratrol (viamethacryloyl chloride), and epoxy-functionalized resveratrol (viaepichlorohydrin) which can be used to react with the appropriate moietyin the polymeric resin.

The process 400 includes dimerizing the functionalized material to forma dimerized material with orthogonal functionality, at 404. For example,the second chemical reaction depicted at the bottom of FIG. 2illustrates the dimerization of the allyl-functionalized resveratrolformed in the first chemical reaction using ultraviolet light (e.g., ata wavelength of at least 300 nm), resulting in a resveratrol dimer withan orthogonal functionality.

The process 400 includes utilizing the dimerized material with theorthogonal functionality during formation of a microcapsule (having anencapsulated payload), at 406. For example, resveratrol dimer with theorthogonal functionality depicted in FIG. 2 may be utilized during theprocess of forming the microcapsules (having the encapsulated payload)depicted in FIG. 1. As described further herein, the payload filledmicrocapsules containing the orthogonal functionality depicted in FIG. 1may be formed using an oil-in-water emulsion technique to create aprotective polymeric shell around a payload core.

In the particular embodiment depicted in FIG. 4, the process 400 alsoincludes incorporating the microcapsule with the orthogonalfunctionality into a polymeric matrix material, at 408. For example,referring to the left side of the chemical reaction diagram depicted inFIG. 3, a first portion of the orthogonal groups of the dimerizedresveratrol material of FIG. 2 may be bound within the microcapsuleshell and a second portion of the orthogonal groups may be bonded to thepolymeric matrix material.

In the particular embodiment depicted in FIG. 4, the process 400 alsoincludes rupturing the microcapsule shell (including the dimerizedmaterial with the orthogonal functionality) via a retro-dimerizationreaction, at 410. For example, as illustrated and further describedherein with respect to FIG. 3, retro-dimerization (e.g., via applicationof UV light at a wavelength <240 nm) may result in rupture of themicrocapsule shell material and associated release of the encapsulatedpayload. Alternatively, as described further herein, in some cases, themicrocapsule shell may rupture via mechanical means, and exposure to UVlight (e.g., sunlight) may result in degradation of the remainingmicrocapsule shell material.

Thus, FIG. 4 illustrates an example of a process of forming a polymericmaterial that includes a microcapsule (having an encapsulated payload)having orthogonal functionality that is bonded to the polymericmaterial. FIG. 4 further illustrates that the microcapsules that arebonded to the polymeric material may be ruptured (or subsequentlydegraded after mechanical rupture) via retro-dimerization when exposedto UV light.

It will be understood from the foregoing description that modificationsand changes may be made in various embodiments of the present inventionwithout departing from its true spirit. The descriptions in thisspecification are for purposes of illustration only and are not to beconstrued in a limiting sense. The scope of the present invention islimited only by the language of the following claims.

What is claimed is:
 1. A process comprising: functionalizing aresveratrol molecule to form a functionalized material; dimerizing thefunctionalized material to form a resveratrol dimer with an orthogonalfunctionality, the orthogonal functionality including an allyl group, avinyl group, a (meth)acrylate group, or an epoxy group; and utilizingthe resveratrol dimer with the orthogonal functionality during formationof a microcapsule that encapsulates a payload agent.
 2. The process ofclaim 1, wherein dimerizing the functionalized material includesapplying ultraviolet (UV) light having a wavelength that is greater than300 nm.
 3. The process of claim 1, wherein the payload agent includes aperfume oil, a repellant, a self-healing agent, or a disinfectant. 4.The process of claim 1, further comprising incorporating themicrocapsule into a polymeric matrix material.
 5. A process comprisingrupturing a microcapsule shell material of a microcapsule to release anencapsulated payload agent via a retro-dimerization reaction, whereinthe microcapsule shell material includes a resveratrol dimer with anorthogonal functionality, the orthogonal functionality including anallyl group, a vinyl group, a (meth)acrylate group, or an epoxy group.6. The process of claim 5, wherein the retro-dimerization reaction isinitiated via application of ultraviolet (UV) light having a wavelengththat is less than 240 nm.
 7. The process of claim 6, wherein the UVlight includes sunlight.
 8. The process of claim 5, wherein theencapsulated payload agent includes a perfume oil, a repellant, aself-healing agent, or a disinfectant.
 9. The process of claim 5,wherein the microcapsule is incorporated into a polymeric matrixmaterial.
 10. A microcapsule that encapsulates a payload agent, themicrocapsule having a microcapsule shell material that is rupturable viaa retro-dimerization reaction, wherein the microcapsule shell materialincludes a resveratrol dimer with an orthogonal functionality, theorthogonal functionality including an allyl group, a vinyl group, a(meth)acrylate group, or an epoxy group.
 11. The microcapsule of claim10, wherein the retro-dimerization reaction is initiated via applicationof ultraviolet (UV) light having a wavelength that is less than 240 nm.12. The microcapsule of claim 10, wherein the encapsulated payload agentincludes a perfume oil, a repellant, a self-healing agent, or adisinfectant.
 13. The process of claim 1, wherein the functionalizedmaterial includes an allyl-functionalized resveratrol material havingthe following chemical structure:


14. The process of claim 13, wherein the resveratrol dimer with theorthogonal functionality has the following chemical structure:


15. The process of claim 5, wherein the resveratrol dimer with theorthogonal functionality has the following chemical structure:


16. The microcapsule of claim 10, wherein the resveratrol dimer with theorthogonal functionality has the following chemical structure: